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WO2008110652A1 - Procédé de stabilisation de plâtre - Google Patents

Procédé de stabilisation de plâtre Download PDF

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Publication number
WO2008110652A1
WO2008110652A1 PCT/ES2008/070041 ES2008070041W WO2008110652A1 WO 2008110652 A1 WO2008110652 A1 WO 2008110652A1 ES 2008070041 W ES2008070041 W ES 2008070041W WO 2008110652 A1 WO2008110652 A1 WO 2008110652A1
Authority
WO
WIPO (PCT)
Prior art keywords
plaster
desulfurization
gypsum
aluminum oxide
fluorine
Prior art date
Application number
PCT/ES2008/070041
Other languages
English (en)
Spanish (es)
Inventor
Esther ÁLVAREZ AYUSO
Javier Querol Carceller
Juan Carlos Ballesteros Aparicio
Antonio JIMÉNEZ ALONSO
Alfedro TOMÁS TELLO
Original Assignee
Endesa Generación, S.A.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Endesa Generación, S.A. filed Critical Endesa Generación, S.A.
Priority to EP08718477.6A priority Critical patent/EP2133310A4/fr
Publication of WO2008110652A1 publication Critical patent/WO2008110652A1/fr
Priority to US12/530,999 priority patent/US20100111821A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/46—Sulfates
    • C01F11/468—Purification of calcium sulfates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/46—Sulfates
    • C01F11/464—Sulfates of Ca from gases containing sulfur oxides
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B11/00—Calcium sulfate cements
    • C04B11/005—Preparing or treating the raw materials
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B11/00—Calcium sulfate cements
    • C04B11/26—Calcium sulfate cements strating from chemical gypsum; starting from phosphogypsum or from waste, e.g. purification products of smoke
    • C04B11/262—Calcium sulfate cements strating from chemical gypsum; starting from phosphogypsum or from waste, e.g. purification products of smoke waste gypsum other than phosphogypsum
    • C04B11/264—Gypsum from the desulfurisation of flue gases
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
    • C04B40/0028—Aspects relating to the mixing step of the mortar preparation
    • C04B40/0039—Premixtures of ingredients
    • E—FIXED CONSTRUCTIONS
    • E21—EARTH OR ROCK DRILLING; MINING
    • E21F—SAFETY DEVICES, TRANSPORT, FILLING-UP, RESCUE, VENTILATION, OR DRAINING IN OR OF MINES OR TUNNELS
    • E21F15/00—Methods or devices for placing filling-up materials in underground workings
    • E21F15/005—Methods or devices for placing filling-up materials in underground workings characterised by the kind or composition of the backfilling material
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/91—Use of waste materials as fillers for mortars or concrete

Definitions

  • the present invention relates to a process for the reduction or elimination of the soluble content of contaminants in gypsum, or in compounds containing gypsum, comprising the mixture of said gypsum, or compound containing gypsum, with additives containing, or are capable to generate, aluminum oxide. More specifically, gypsum is the process of gas desulfurization and the contaminant is fluorine.
  • This aspect may entail both environmental risks and high costs in the management of this waste by thermal power plants in the event that said limit was exceeded and then the desulfurization plaster was characterized as a material only acceptable in hazardous waste landfills. .
  • the present invention relates to a plaster stabilization method, in particular that generated in the desulfurization process, of coal-fired power plants, for deposit in landfills or for use as filler material in mine rehabilitation or for other apps.
  • This stabilization method has the objective of reducing the leaching of minor pollutants and trace, as for example, the fluorine present in the plaster desulfurization, ensuring the characterization of this by-product as acceptable material in non-hazardous waste landfills in accordance with current legislation (Decision 2003/33 / EC), and thus reducing the corresponding environmental risks and economic implications that would entail for thermal power plants The management of a waste characterized as only acceptable in hazardous waste landfills.
  • the solution provided by this invention is based on the use of products containing or generating aluminum oxide, in particular amorphous aluminum oxide, as additives prior to the discharge of the desulfurization plaster, or prior to its formation in the plant absorber desulfurization
  • Amorphous aluminum oxide is capable of immobilizing minor and trace pollutants, such as fluorine, in an appreciable amount by adsorption processes on its surface, so that a significant reduction in its leaching is achieved, thus avoiding the consequences that its leaching It involves the discharge of the desulfurization plaster.
  • the gypsum generated in the desulfurization plants of the thermal power plants is basically constituted by this mineral (CaS ⁇ 4-2H 2 O), although accompanying it, other minerals are also present, but in a much smaller amount, resulting from the interaction of other components (other than SO 2 ) present in the gaseous emissions of coal-fired power plants and limestone slurry present in the desulfurization plants absorber.
  • the fluorine retained by the limestone slurry is present in the fluorite desulfurization plaster (CaF 2 ), the solution of this mineral being responsible for the leaching of the fluoride from the desulfurization plaster.
  • one aspect of the present invention relates to a process for the reduction or elimination of the soluble content of contaminants and therefore, of its leachable fraction.
  • contaminants are those capable of reacting with aluminum oxide through adsorption processes. More preferably, the contaminant is fluorine.
  • the plaster or the compounds containing plaster are mixed with additives that contain or are capable of generating aluminum oxide.
  • the gypsum (or gypsum-containing compounds) is from the desulfurization processes. In these desulfurization processes gypsum-rich by-products are generated that are mixed, before or after the desulfurization process, with the additives that contain or are capable of generating aluminum oxide, in the desulfurization plant absorber.
  • the mixture of additives, providing the aluminum oxide, with the desulfurization plaster can be carried out prior to its pouring, that is, once the filtering stage of the plaster slurry has been carried out.
  • Any known mixing method that achieves a more or less homogeneous distribution of both components may be suitable to perform this step of adding the minor pollutants and trace immobilizing agent, such as fluoride to the desulfurization plaster.
  • An additional advantage is that, after its incorporation, it is not necessary to carry out any other treatment on the mixture, nor is it necessary any waiting time after mixing and prior to pouring.
  • the additive providing the aluminum oxide
  • the additive can be incorporated into the desulfurization plant absorber prior to the formation of the desulfurization plaster, provided that the amount to be incorporated is sufficiently reduced as so as not to alter the desulfurization process itself, and not alter the pH conditions required in the desulfurization stage, which will be marked by the type of additive to be incorporated in order to immobilize minor contaminants and trace as fluorine.
  • the additives are materials that contain or generate aluminum oxide and are selected from among, aluminum oxide, the ashes from coal-fired power plants, aluminum salts (or soluble species that release aluminum), or compounds containing prehydrolyzed forms of aluminum. More preferably, the aluminum oxide contained or generated in these materials is amorphous. Amorphous aluminum oxide has a large number of hydroxyl groups on its surface that can lead to adsorption processes of different elements, and in particular of high electronegativity halides, as is specifically the case with fluoride. Amorphous aluminum oxide is present in a significant proportion in the ashes generated by coal-fired power plants. Generally, these ashes have as a majority component the glass where precisely the amorphous aluminum oxide is found.
  • amorphous aluminum oxide can be easily produced from solutions of aluminum salts (or soluble species that release aluminum) by neutralizing them, thus resulting in the precipitation of said oxide.
  • aluminum salts or soluble species that release aluminum
  • sulfates, chlorides and bicarbonates can preferably be used, but not limited to these.
  • the amount to be incorporated of amorphous aluminum oxide to stabilize the desulfurization plaster can vary greatly depending on the levels of immobilization of minor contaminants and trace (such as fluorine) that are to be achieved, and can range from very low incorporation values 0.02- 0.1% to still relatively low values around 5%;
  • the percentage of minor contaminants and immobilized traces, such as fluoride, increases with the percentage of amorphous aluminum oxide incorporated.
  • the values of incorporation of amorphous aluminum oxide are dependent on the source that supplies the amorphous aluminum oxide, which implies that the levels of oxide incorporation amorphous aluminum can be increased.
  • the level of incorporation of amorphous aluminum oxide will be determined by the level of immobilization of minor pollutants and trace, such as fluorine, which is to be achieved and by the source that supplies the amorphous aluminum oxide.
  • the amount of pure aluminum oxide that is used in total mixing is variable depending on the reduction of the leachable fraction of the contaminant to be achieved.
  • the amount of aluminum oxide to be used is less than or equal to 10% by weight of the total mixture and more preferably less than or equal to 5%. If ashes from thermal power plants of carbon, the amount of ashes to be used is less than or equal to 60% by weight of the total mixture, preferably an amount less than or equal to 50% by weight of the total mixture.
  • aluminum salts are used, and more particularly aluminum sulfate, the amount of aluminum salts to be used is less than or equal to 20% by weight of the total mixture. Particularly, an amount less than or equal to 15% by weight of the total mixture
  • a second aspect refers to the plaster, or compounds containing plaster, obtainable by the method described in the present invention.
  • a third aspect of the present invention refers to the use of plaster, or compounds containing plaster, as a construction material or for use as a filler material in the rehabilitation of mines. In addition to these applications, it can also be taken to landfills for deposit.
  • the leaching studies according to the European standard EN 12457-4 involve the realization of a stirring period of 24 h using deionized water as an extractant in a liquid / solid ratio of 10 l / kg dry mass. Based on the leaching studies, Decision 2003/33 / EC classifies waste for acceptance in landfills. According to this classification, and according to the leachable content of trace contaminants, a material is acceptable in landfills of non-hazardous waste if the leachable content of trace contaminants does not exceed certain limits (for example for fluorine this limit is 150 mg / kg mass dry).
  • the pure amorphous aluminum oxide used in the stabilization of the desulfurization plaster was synthesized in the following way: a solution of 2M NaOH was slowly added to a solution of 1.5M AICI3 in a ratio of 2: 1 volumes under continuous stirring. . The resulting precipitate was repeatedly washed with deionized water, filtered and dried at 70 0 C for 24 h. The precipitated solid was characterized as amorphous aluminum oxide by X-ray diffraction (DRX).
  • the samples were homogenized by stirring them by means of a flip shaker (10 rpm) for 5 minutes. Subsequently, the samples thus treated were evaluated with respect to their leaching behavior following the European standard EN 12457-4.
  • the leachable content of fluoride in the different treated samples, as well as the percentage of immobilization of fluoride achieved with respect to the untreated desulfurization plaster is indicated in Table 2.
  • the levels of immobilization, and therefore the levels of reduction of the leachable fluorine content, are dependent on the percentage of pure amorphous aluminum oxide added. Immobilization levels greater than 90% are obtained using doses of pure amorphous aluminum oxide of 5%, reducing the leachable fluorine content to values of 10 mg / kg.
  • EXAMPLE 3 Obtaining ashes from coal-fired power plants.
  • the aluminum sulfate used in the stabilization of the desulfurization gypsum is commercial AI 2 (SO 4 ) 3 -18 H 2 O.
  • n.d. means not detectable.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Structural Engineering (AREA)
  • Materials Engineering (AREA)
  • Geology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Mining & Mineral Resources (AREA)
  • Inorganic Chemistry (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Processing Of Solid Wastes (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Treating Waste Gases (AREA)

Abstract

L'invention concerne un procédé de réduction ou d'élimination du contenu soluble de polluants du plâtre, ou de composés contenant du plâtre, consistant à mélanger ledit plâtre ou composé contenant du plâtre avec des additifs contenant ou pouvant générer de l'oxyde d'aluminium. Plus spécifiquement, le plâtre est le résultat du processus de désulfuration de gaz et le polluant est le fluor.
PCT/ES2008/070041 2007-03-12 2008-03-07 Procédé de stabilisation de plâtre WO2008110652A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP08718477.6A EP2133310A4 (fr) 2007-03-12 2008-03-07 Procédé de stabilisation de plâtre
US12/530,999 US20100111821A1 (en) 2007-03-12 2009-03-07 Gypsum stabilisation method

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ES200700639A ES2304218B1 (es) 2007-03-12 2007-03-12 Procedimiento para estabilizar yeso.
ES200700639 2007-03-12

Publications (1)

Publication Number Publication Date
WO2008110652A1 true WO2008110652A1 (fr) 2008-09-18

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/ES2008/070041 WO2008110652A1 (fr) 2007-03-12 2008-03-07 Procédé de stabilisation de plâtre

Country Status (4)

Country Link
US (1) US20100111821A1 (fr)
EP (1) EP2133310A4 (fr)
ES (1) ES2304218B1 (fr)
WO (1) WO2008110652A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6385110B2 (ja) * 2013-04-08 2018-09-05 一般財団法人電力中央研究所 石膏からのフッ素溶出量分析方法
CN105868510A (zh) * 2016-04-29 2016-08-17 中国矿业大学 一种充填采煤的充填体压实成形密度设计确定方法
CN112479614B (zh) * 2020-12-01 2022-06-10 济南大学 一种固化石膏中可溶性磷和氟的处理剂及其固化方法与应用

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0124574A1 (fr) 1982-10-29 1984-11-14 Wahlbeck H G E Procede et dispositif de fabrication d'objets en metaux precieux anallergiques.
WO2001070377A1 (fr) * 2000-03-21 2001-09-27 Elsamprojekt A/S Composition d'acides organiques, procedes de preparation et d'utilisation de cette composition dans des usines de desulfuration produisant du gypse
JP2004299962A (ja) * 2003-03-31 2004-10-28 Central Res Inst Of Electric Power Ind 石こう中のフッ素の除去方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3704731C3 (de) * 1986-02-20 1993-12-02 Hoelter Heinz Flotationsbergeversatz
JP2934549B2 (ja) * 1992-02-03 1999-08-16 三菱重工業株式会社 排ガスの処理方法
JPH07136615A (ja) * 1993-11-22 1995-05-30 Entetsuku:Kk 有害金属含有飛散灰を無害安定化するための処理剤、及び処理方法
JP3382202B2 (ja) * 2000-03-10 2003-03-04 独立行政法人産業技術総合研究所 フッ素不溶出性石膏組成物とその製造方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0124574A1 (fr) 1982-10-29 1984-11-14 Wahlbeck H G E Procede et dispositif de fabrication d'objets en metaux precieux anallergiques.
WO2001070377A1 (fr) * 2000-03-21 2001-09-27 Elsamprojekt A/S Composition d'acides organiques, procedes de preparation et d'utilisation de cette composition dans des usines de desulfuration produisant du gypse
JP2004299962A (ja) * 2003-03-31 2004-10-28 Central Res Inst Of Electric Power Ind 石こう中のフッ素の除去方法

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Derwent World Patents Index; AN 2004-760924, XP008113597 *
E. ALVAREZ-AYUSO ET AL., CHEMOSPHERE, vol. 65, 2006, pages 2009 - 2017
See also references of EP2133310A4

Also Published As

Publication number Publication date
EP2133310A4 (fr) 2015-05-20
ES2304218A1 (es) 2008-09-16
ES2304218B1 (es) 2009-09-14
US20100111821A1 (en) 2010-05-06
EP2133310A1 (fr) 2009-12-16

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